Unsaturated zwitterionic surface active compounds

ABSTRACT

ZWITTERIONIC SURFACE ACTIVE COMPOUNDS ARE PROVIDED HAVING THE FOLLOWING FORMULA:   R1-Z(+)(-R2)(-R3)-CH2-CH=CH-CH2-SO3-(-)   WHEREIN R1 REPRESENTS AN UNSATURATED OR SATURATED ALIPHATIC GROUP HAVING 6 TO 24 CARBON ATOMS, R2 AND R3 EACH REPRESENT AN ALKYL GROUP HAVING 1 TO 6 CARBON ATOMS, AND Z REPRESENTS NITROGEN OR PHOSPHORUS. THESE COMPOUNDS HAVE VALUABLE SURFACE ACTIVE PROPERTIES THAT MAKE THEM ESPECIALLY USEFUL AS DETERGENT COMPOUNDS.

United States Patent 3,825,588 UNSATURATED ZWITTERIONIC SURFACE ACTIVECOMPOUNDS Melvin A. Barbera, Mount Healthy, Ohio, assignor to TheProcter & Gamble Company, Cincinnati, Ohio No Drawing. Originalapplication Mar. 31, 1970, Ser. No.

24,330, now Patent No. 3,668,240. Divided and this application Apr. 28,1972, Ser. No. 248,765

Int. Cl. C07c 143/16 U.S. Cl. 260--513 R 2 Claims ABSTRACT OF THEDISCLOSURE Zwitterionic surface active compounds are provided having thefollowing formula:

l RsH H wherein R represents an unsaturated or saturated aliphatic grouphaving 6 to 24 carbon atoms, R and R each represent an alkyl grouphaving 1 to 6 carbon atoms, and Z represents nitrogen or phosphorus.

These compounds have valuable surface active properties that make themespecially useful as detergent compounds.

CROSS REFERENCE This application is a division of application Ser. No.24,330 filed Mar. 31, 1970 and titled Unsaturated Zwitterionic SurfaceActive Compounds now US. Pat. 3,668,240.

BACKGROUND OF THE INVENTION (1) Field of the Invention This inventionrelates tozwitterionic surface active compounds which are useful asdetergents. The zwitterionic surface active compounds are characterizedby having an unsaturated double bond located in the mole cule betweenthe anionic and cationic groups.

(2) Prior Art Zwitterionic or internally neutralized surface activecompounds having both anionic and cationic groups are known. They areusually depicted as having a formula R R R N R X in which the Rs arealkyl or alkylene groups (R, always being saturated aliphatic) and X isCOO- or SO No previous disclosure has been found of a surface activecompound having R representing a group CH CH=CH-CH It is this uniquemolecular arrangement which distinguishes the compounds of the presentinvention from prior art zwitterionic surface active compounds. It hasbeen surprisingly discovered that the presence of the double bondcontributes unexpectedly to the detergent properties of this molecule.

SUMMARY OF THE INVENTION The compounds of the present invention have theformula in which R represents an unsaturated or saturated aliphaticgroup having 6 to 24 carbon atoms, preferably a saturated group having 8to 18 carbon atoms, R, and R each represent an alkyl group having 1 to 6carbon atoms, preferably 1 to 3 carbon atoms, and Z is selected fromnitrogen or phosphorus, preferably nitrogen.

This class of compounds is illustrated by the following specificexamples:

4 (N,N dimethyl-N-hexadecyl-ammonio)-2-butenel-sulfonate; 4-(N,N-dimethyl-N-alkylammonio -2-butenel-sulfonate, the alkyl groupderived from tallow fatty alcohol;4-(N,N-diethyl-N-hexadecylammonio)-2-butene-1- sulfonate; 4(N,N-diethyl-N-tetradecyl-ammonio)-2-butene l-sulfonate;4-(N,N-dimethyl-N-alkylammonio)-2- butene-l-sulfonate, the alkyl groupbeing derived from the middle cut of coconut fatty alcohol;4-(N,N-dimethyl-N- octadecylammonio) 2 butene-l-sulfonate;4-(N-2-hydroxyethyl, N-methyl, N-tetradecylammonio)-2-butene-lsulfonate; 4 (N,N-dimethyl-N-dodecylammonio)-2-butene l-sulfonate;4-(N,N-dimethyl-N-hexadecylphosphonio)-2-butene-l-sulfonate;4-(N,N-dimethyl-N-alkylphosphonio) 2-butene-1-sulfonate, the alkyl groupderived from the middle cut of coconut fatty alcohol; and 4-(N, Ndiethyl-N-hexadecylphosphonio -2-butene-1-sulfonate. Specific referenceto the above compounds is given only for the purpose of illustration,and it will be appreciated that many other similar variations may beused in this invention so long as the general formula requirements areobserved.

The preferred compounds of this invention are 4-(N,N- dimethyl Nhexadecyl-ammonio)-2-butene-1-sulfonate; 4 (N,Ndimethyl-N-alkylammonio)-2-butene-1-sulfomate in which the alkyl groupis tallow alkyl which approximately consists of a mixture of 66% C 30% C4% C or in which the alkyl group is middle cut coconut fatty alkyl whichapproximately consists of a mixture of 2% C 66% C 23% C and 9% C It ispreferred that R and R be selected from methyl, ethyl, propyl,isopropyl, butyl and ethanol.

The unsaturated zwitterionic compounds of the present invention can bemade by any convenient method or process. For example, they can beprepared by reacting tertiary amines or phosphines with butene sultones.The butene sultone can be from any source but a ready source is by asulfonation reaction between 1,3-butadiene and an SO -dioxane complex.

An SO -dioxane complex can be prepared by the following procedure:

The complex readily precipitates out, and is then filtered and washedwith dioxane. The filter cake is then ordinarily slurried in dioxane,and butadiene is bubbled through the slurry until all of the solids havedisappeared. To the reaction product containing a butene sultonecompound and a sulfonated butene polymer is added either a tertiaryamine or phosphine compound, e.g., dodecyl dimethyl amine. The reactionproceeds at reflux and a reaction product is formed containing thedesired 4-(N, N-dialkyl-N-alkyl) 2 butene-l-sulfonate in substantialyield. NMR and IR analyses have confirmed the desired reaction product.

EXAMPLE g. S0 were added to a mixture of 212 g. dioxane and 588 g.ethylene dichloride. A white solid precipitate which formed was removedby filtering. The precipitate was added to 650 g. dioxane, the mixturewas heated to 60 C. and butadiene was bubbled in until the solids werereacted. A two phase liquid resulted. The bottom phase, a yellow oil,was added slowly to 474 g. dimethyldodecylamine and 1308 g. acetone.This mixture was refluxed at 59 C. and amine values were taken to followthe reaction. Time 0 minutes on amine values is after addition;theoretical value is 56.

3 Time: Amine value minutes 43 30 minutes 40 90 minutes 42.4 180 minutes41.9 300 minutes 42.5

The material was then chilled in a 0 F. box overnight and the whitesolids removed by filtering and washed with acetone. The solids weredissolved in a 50% 3 A alcohol in water solution to 20% solids level.The pH was raised to about 9 with 50% NaOH in order to free the aminefrom the salt form. This was then filtered to remove the sodium saltsand washed with petroleum ether then dried to a solids form. Thematerial was then redissolved to a 62% volatiles-38% solids level withwater. Analysis confirmed a reaction product of 4-(N dodecyl-N,N-dimethyl) 2 butene 1 sulfonate.

The discovery that the introduction of one double bond into the radicalbetween cation and anion groups of a zwitterion as described hereinproduces a compound having surface active performance superior to thatof its saturated four carbon counterpart was totally unexpected. Thedouble bond, believed to be the cis-stereoisomer, apparently allowspositioning of the charged zwitterionic groupings in such a manner as toenhance the surface activity of the unsaturated compounds beyond that oftheir saturated counterparts.

In preparing detergent compositions, especially valuable as launderingcompositions, it is desirable to use the unsaturated zwitterionicsurface active compounds of this invention in admixture with detergencybuilder compounds. Excellent compositions consist of an unsaturatedzwitterionic detergent compound of this invention and at least onedetergency builder selected from inorganic or organic alkaline buildersin a proportion by weight of detergent to builder of 10:1 to 1:20 andpreferably from 5:1 to 1:10. These compositions provide best overalllaundering results including soil removal and whiteness maintenanceresults when used in washing solutions having a pH 6.5 to 11.5,preferably 7 to 11, optionally 8.5-11.

Water soluble inorganic alkaline builder salts which can be used in thisinvention alone or in admixture are alkali metal carbonates, borates,phosphates, polyphosphates, bicarbonates and silicates. Ammonium orsubstituted ammonium, e.g., triethanol ammonium, salts of thesematerials can also be used. Specific examples of suitable salts aresodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodiumand potassium pyrophosphate, sodium and ammonium bicarbonate, potassiumtripolyphosphate, sodium hexametaphosphate, sodium sesquicarbonate,sodium orthophosphate and potassium bicarbonate. The preferred inorganicalkaline builders according to this invention are alkali metaltripolyphosphates for built granular compositions.

Examples of suitable organic alkaline sequestrant builder salts used inthis invention alone or in admixture are alkali metal, ammonium orsubstituted ammonium, aminocarboxylates, e.g., sodium and potassiumethylenediaminetetraacetate, sodium and potassium N-(2hydroxyethyl)ethylenediaminetriacetates, sodium and potassium nitrilotriacetates andsodium, potassium and trieethanolammonium N (2 hydroxyethyl)nitrilodiacetates. Mixed salts of these polycarboxylates are alsosuitable. The alkali metal salts of phytic acid, e.g., sodium phytateare also suitable as organic alkaline sequestrant builder salts (see US.Pat. 2,739,942). Sodium ethane 1 -hydroxy, l-diphosphonate, and sodiumcitrate can also be used as builders either alone or in mixtures withother builder compounds. Other suitable builders include methylene andethylene diphosphonates and their derivatives, ethane 1hydroxy-1,1,2-triphosphonate, sodium itaconate, and sodium polymaleateand the like.

The unsaturated zwitterionic surface active compounds of the presentinvention can also be used in combination with other detergent materialsselected from anionic synthetic detergents, nonionic syntheticdetergents and ampholytic and zwitterionic synthetic detergents.

A laundering method incorporating the discovery of the present inventioncan be practiced in a number of different ways. Preferably the washingstep is followed by rinsing and drying the fabrics. The washing solutioncan be prepared by adding the granular, tablet or liquid detergentcomposition prepared according to this invention to any container whichcontains water at a temperature ranging from about 40 F. to about 200F., usually about F. F. The detergent composition concentration insolution can range from about .05% to .50% by total weight, and shouldbe added in sufficient amount to provide a concentration of at least0.005% of the zwitterionic detergent compound. The fabrics can be addedto the container or washer before or after the washing solution isadded. As is usual in a washing step, the fabrics are then agitated inthe detergent solution. While the period of time may vary, an automaticagitator type washer, generally employs a washing cycle which rangesfrom 8 to 15 minutes.

After the washing step, the washing liquor is drained ofi" or thefabrics are separated from the liquor and thereafter the fabrics arerinsed in clean water. The fabrics can be rinsed as many times asdesired in order to insure that washing liquor is removed. Using anautomatic washer, it has been found that about four spray rinses and onedeep rinse are usually sufficient for this purpose. Between and afterrinsing steps, the bulk of the rinse water is usually drawn from, orspun out of the fabrics. After rinsing, the fabrics are dried. Althoughrinsing and drying are usual and desirable steps, the importantadvantage of the invention is achieved in the washing step.

The following compositions will illustrate the manner in which thezwitterionic surface active detergent compounds of this invention can beused. Included are both liquid and granular formulations. It will beunderstood, however, that the examples are not to be construed orlimiting the scope of conditions claimed hereinafter. These compositionsare useful in automatic washers and conventional type washers as well ashand washing operations.

EXAMPLE OF GRANULAR BUILT DETERGENT COMPOSITIONS Percent 4 (N,Ndimethyl-N-hexadecylammonio)-2-butene-l-sulfonate 7 Sodiumnitriolotriacetate 50 Sodium xylene sulfonate 5 Sodium silicate (NaO:SiO =l:2.5) 7 Fluorescent dye .16 Perfume .2 Benzotriazole .02 Sodiumsulfate 20.62

Water and minor amounts of miscellaneous material 10 EXAMPLE OF BUILTLIQUID DETERGENT COM-POSITION Percent 4-(N,N-dimethyl Nalkylammonio*)-2-butenel-sulfonate 12 Tetrapotassium pyrophosphate 20Sodium silicate (Na O:SiO =1:l.6 3.8 Potassium toluene sulfonate 8.5Sodium carboxymethyl hydroxy ethyl cellulose .3 Fluorescent dye .12Perfume .15

Benzotriazole .02

Water 55.11

*Alkyl referring to the R1 group derived from the middle guyt 06.foconut fatty alcohol (2% C10, 66% C12, 23% C14,

EXAMPLE OF BUILT LIQUID DETERGENT COMPOSITION Percent 4-(N,N-dimethyl Ntetradecylammonio)-2-bu- *Alkyl referring to the R1 group obtained fromtallow fatty alcohol (66% 01s, 30% C111, 4% C14) and others.

EXAMPLE OF GRANULAR BUILT DETERGENT COMPOSITION Percent 4-(N,N-dimethylN alkylammonio*)-2-butene-1 sulfonate 17 Sodium citrate 28 Sodiumtripolyphosphate 25 Sodium silicate (Na O:SiO =1:2.5) 6 Sodium toluenesulfonate 2 Sodium carboxy methyl cellulose .3 Sodium sulfate 13Fluorescent dye .16 Water 8 Protease enzyme .54

*Alkyl referring to the R1 group obtained from tallow fatty alcohol (66%C111, 30% C10, 4% C14) and others.

EXAMPLE OF LIQUID BUILT DETERGENT COMPOSITION Percent 4-(N,N-dimethyl Nalkylammonio*)-2butene-1- sulfonate 10 Sodium pyrophosphate 60 Sodiumsilicate (Na O:SiO =1:2.5) 6 Sodium toluene sulfonate 2 Sodium carboxymethyl cellulose .3 Water 11.3 Miscellaneous (fluorescers, perfume,anti-tarnish agents, sodium sulfate, etc.) Balance *Alkyl referring tothe R1 group obtained from tallow fatty alcohol (66% C111, 30% Cm, 4%C14) and others.

EXAMPLE OF GRANULAR BUILT DETERGENT COMPOSITION Percent 4-(N,N-diethyl Nalkylammonio 2 butene-lsulfonate 17 Sodium citrate 45 Sodium silicate(Na O:SiO- =1:2.5) 6 Sodium carboxy methyl cellulose .5 Sodium sulfate28 Water 3.5

*Alkyl referring to the R1 group derived from the middle gu /t 0C5)coconnt fatty alcohol (2% C10, 66% C12, 23% C11,

6 EXAMPLE OF LIQUID BUILT DETERGENT COMPOSITION Percent 4-(N,N-diethyl Nhexadecylammonio)-2-butene-lsulfonate 12 Sodium nitrilotriacetate 19Sodium silicate (Na O:SiO =1:1.6) 3.8 Sodium carboxy methyl cellulose .3Water 63 Miscellaneous Balance It will be appreciated that theunsaturated zwitterionic compounds used in the present invention can beincorporated into liquid or granular detergent compositions withsuitable adjustments being made in the other components.

Materials which are considered normal and desirable additives in liquidor granule detergent compositions can also be added to the compositionsof this invention without substantially modifying the basiccharacteristics of the unsaturated zwitterionic detergent surfactants.For example, a tarnish inhibitor such as benzotriazole or ethylenethio-urea may be added in amounts up to about 1%. Fluorescers, perfume,color, enzymes, antiredeposition agents, thickening agents, opacifiers,other detergent compounds, and blending or viscosity control agents,while not essential in the compositions of this invention, may also beadded.

The zwitterionic surface active compounds of the present invention areespecially valuable because of their excellent overall soil removingproperties. In addition, these compounds possess excellent whitenessmaintenance properties when used in combination with the buildercompounds described above. Detergency tests have demonstrated that theunsaturated zwitterionic compounds of the present invention provideoverall detergency at least equivalent to such an excellent detergent assodium tallow alkyl sulfate and 3-(coconut alkyl dimethylammonio)-2-hydroxy-1-sulfonate.

What is claimed is:

1. An unsaturated zwitterionic surface active compound having theformula References Cited UNITED STATES PATENTS 3/1958 Gaertner 260513 RX 6/1972 Barbera 2605l3 R X LEON ZITVER, Primary Examiner N. CHAN,Assistant Examiner

